EP3110534B1 - Reinigungsverfahren für teilweise hydrolysierte cellulose - Google Patents

Reinigungsverfahren für teilweise hydrolysierte cellulose Download PDF

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Publication number
EP3110534B1
EP3110534B1 EP14884237.0A EP14884237A EP3110534B1 EP 3110534 B1 EP3110534 B1 EP 3110534B1 EP 14884237 A EP14884237 A EP 14884237A EP 3110534 B1 EP3110534 B1 EP 3110534B1
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EP
European Patent Office
Prior art keywords
electrodialysis
acid
composition
partly
cell
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EP14884237.0A
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English (en)
French (fr)
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EP3110534A4 (de
EP3110534A1 (de
Inventor
James M. LOCKHART
Peter G. Symons
J. David Genders
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Noram Engineering and Constructors Ltd
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Noram Engineering and Constructors Ltd
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Priority to PT148842370T priority Critical patent/PT3110534T/pt
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Publication of EP3110534A4 publication Critical patent/EP3110534A4/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • B01D61/423—Electrodialysis comprising multiple electrodialysis steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D5/00—Purification of the pulp suspension by mechanical means; Apparatus therefor

Definitions

  • electrodialysis it is known to use electrodialysis for the de-ionization of water and of solutions containing non-charged dissolved species, such as proteins.
  • electrodialysis can affectively be used to remove acid from compositions of partly-hydrolyzed cellulose.
  • FIG. 7 schematically depicts an electrodialysis cell configuration having anion-specific membranes A and cation-specific membranes C.
  • Figure 11 schematically depicts an electrodialysis cell configuration having bi-polar membranes B and anion-specific membranes A.
  • an anionic resin is placed in the feed compartments of the electrodialysis cell, the cell having either an anion-bipolar membrane configuration or an anion-cation membrane configuration. This increases the feed conductivity and sulfate transfer rate, especially at low free sulfate levels.
  • the acid in the composition of partly-hydrolyzed cellulose particles and acid is neutralized prior to electrodialysis. This can be done at any desired stage of the process by the addition of base, for example prior to any dilution or dialysis, or immediately before electrodialysis by adding the base to the feed compartment of the electrodialysis cell.
  • the neutralized composition is then processed in accordance with the methods described above, resulting in the purified partly-hydrolyzed cellulose particles and a waste stream of salt solution rather than an acid.
  • a suspension of partly-hydrolyzed cellulose particles in sulfuric acid was produced as follows. 115 g of finely ground Kraft pulp were reacted with 1600 g of 64% H 2 SO 4 in a continuously mixed beaker at a temperature of 45°C for 35 minutes. This mixture was then quenched with about 5 L of room temperature de-ionized (DI) water to make-up to a total of 6.0L. The suspension was then allowed to settle for several hours. Once a clean supernatant layer was obtained it was decanted off, and DI water added again to make back up to 6.0L. The settle, decant, re-dilute procedure was repeated 8 times until the suspension no longer settled significantly.
  • DI room temperature de-ionized
  • the AAV membrane A is a specialty membrane developed to help prevent proton back-migration.
  • the sulfate travels across the anion membrane. This removes the sulfate from the feed solution, which then combines with the proton crossing the cation membrane to increase the acid strength in the receiving compartment.
  • the cell was charged at a constant 3.2 V across the platinum wire probes (four cation and four anion membranes).
  • the overall current efficiency was 79%, with very good correlation between feed and receiving current efficiencies.
  • the current efficiency dropped throughout the run as the feed was depleted and the acid concentration increased in the receiving compartment.
  • 0.18 M sulfuric acid was obtained, it is predicted that the low concentration of sulfate in the feed increases the voltage drop on the AAV membrane significantly which may increase the amount of proton back migration.
  • the target conductivity and pH were met, the sulfate level was about 10 times higher than the amount predicted at these levels, which may be due to the solids content of this solution.
  • the cell was disassembled and examined for signs of solids pluggage and membrane fouling; surprisingly no visible signs of solids deposition were observed in this, or any subsequent experiments.
  • the power supply used for these tests had a voltage limit of 10 V, which initially limited the Pt-Pt voltage as the end voltages were high (5 volts total).
  • Figure 12 shows the voltage and current density profiles. As the current density dropped so did the end voltages. At about 0.04 moles of charge, the end voltages dropped below 4.4 V and this allowed the cell to reach 5.6 V between platinum probes. This cell ran at an average current density of 6.0 mA/cm 2 .
  • the active area of the feed flow frames were filled with the resin and the inlet and outlet channels of the frames were filled with glass wool to retain the resin within the cell.
  • the total cell voltage again was limited and the run did not reach 5.6 V between the platinum probes until 0.055 moles of charge has passed as shown in Figure 15 .
  • An average current density of 8.2 mA/cm 2 was obtained.
  • Figure 18 compares the Example 1, 2 and 3 experiments. Overall the electrodialysis was very effective in removing the sulfate from the cellulose solution and no signs of solids pluggage or membrane fouling were observed. By adding the resin in the feed compartment, virtually the entire amount of sulfate was removed. The resin initially removed some sulfate at the beginning of the experiment so that less charge was passed. This is due to the resin starting in the basic form, which would not be the case if a second batch was performed. The resin allowed complete removal of the sulfate at higher current density than the other runs.
  • the free sulfate concentration could be reduced in the first step 30 of electrodialysis from 90mM to 16 mM (about 82% removal) in a back mixed unit with an acidic receiving fluid (to allow re-use of the recovered acid) with an estimated current efficiency of about 72% and current density of about 40 mA/cm 2 .
  • the partially purified partly-hydrolyzed cellulose suspension is then further purified in the second step 82 of electrodialysis (e.g.
  • the first stage 30 may be operated as a batch or plug flow purification to reduce its size and power consumption by approximately half. Also optionally, more stages of electrodialysis could be used, as the greater the number of stages the smaller the impact of using continuously back mixed units as opposed to batch or plug flow ones.
  • any of the stages of electrodialysis may utilize either a dilute acid or partially neutralized feed or receiving solution; it is not necessary for these to be the same.
  • Example 4 A reduction in current density was observed in Example 4 above, which is believed to be due to the reduction in receiving solution conductivity when neutralized. A further reduction in current density is anticipated when the feed is neutralized, given that both feed and receiving fluids would then have reduced solution conductivities.
  • a bi-polar membrane is added between the cation and anion membranes of the receiving fluid in Example 6 in order to regenerate both the original acid and the original base.
  • protons generated at the bi-polar membrane surface recombine with removed anions to regenerate the original acid.
  • the hydroxide formed on the other bi-polar membrane surface combines with the removed cation, regenerating the base used for feed neutralization.
  • a dilution based dialysis system's capacity, flows and cost are roughly proportional to the logarithm of the percentage removal rate required regardless of the absolute concentration or removal.
  • either the first, second or last 10-fold reduction in acid to partly-hydrolyzed cellulose ratio each require about 1/3 the dialysis capacity required to achieve a total 1,000-fold reduction.
  • the sizing and membrane area requirements and cost of the present electrodialysis based purification system have been shown to be much more closely related to the actual quantity of ions removed.
  • the first 10-fold reduction might represent approximately 90% of the cost, compared to only 10%, for the remaining 100 times reduction.
  • the electrodialysis purification system has been found to be particularly well suited toward the final purification of partly-hydrolyzed cellulose where free ion concentrations are already low in absolute terms, but large percentage removal rates are still required.
  • Significant capital, time, water usage and operating cost reductions may be realized through the appropriate use of the electrodialysis purification system; however, in some cases, the optimal overall system configuration may include some dilution dialysis based removal upstream.

Landscapes

  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (16)

  1. Verfahren zur Rückgewinnung von gereinigten, teilweise hydrolysierten Celluloseteilchen aus einer Zusammensetzung, die agglomerierte, teilweise hydrolysierte Celluloseteilchen und freie Ionen enthält, umfassend den Schritt der Elektrodialyse der Zusammensetzung zur Erzeugung eines Stroms, der gereinigte, teilweise hydrolysierte Celluloseteilchen enthält.
  2. Verfahren nach Anspruch 1, wobei die freien Ionen eine Säure umfassen.
  3. Verfahren nach Anspruch 1 oder 2, weiterhin umfassend eine Vorbehandlung der Zusammensetzung vor der Elektrodialyse, um die Konzentration der freien Ionen zu verringern.
  4. Verfahren nach Anspruch 3, wobei die freien Ionen eine Säure umfassen.
  5. Verfahren nach Anspruch 3 oder 4, wobei die Vorbehandlung ein Verdünnen der Zusammensetzung mit einer Wasser enthaltenden Flüssigkeit umfasst.
  6. Verfahren nach Anspruch 3 oder 4, wobei die Vorbehandlung ein Verdünnen der Zusammensetzung mit einer Wasser enthaltenden Flüssigkeit und ein Konzentrieren der verdünnten Zusammensetzung umfasst.
  7. Verfahren nach Anspruch 3 oder 4, wobei die Vorbehandlung ein Verdünnen der Zusammensetzung mit einer Wasser enthaltenden Flüssigkeit, ein Konzentrieren der verdünnten Zusammensetzung und eine Dialyse der konzentrierten Zusammensetzung umfasst.
  8. Verfahren nach Anspruch 3 oder 4, wobei die Vorbehandlung ein Verdünnen der Zusammensetzung mit einer Wasser enthaltenden Flüssigkeit, dann ein Konzentrieren der verdünnten Zusammensetzung, dann ein Verdünnen der konzentrierten Zusammensetzung und dann eine Dialyse der verdünnten Zusammensetzung umfasst.
  9. Verfahren nach einem der vorhergehenden Ansprüche, weiterhin umfassend ein Hinzufügen einer Base zu der Zusammensetzung vor der Elektrodialyse.
  10. Verfahren nach einem der vorhergehenden Ansprüche, weiterhin umfassend ein Hinzufügen einer Base zu einer Empfangslösung einer Elektrodialysezelle vor der Elektrodialyse.
  11. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Elektrodialyse unter Verwendung einer Elektrodialysezelle mit einem der folgenden Elemente durchgeführt wird:
    (a) einer Kation-Anion-Membranzellenkonfiguration;
    (b) einer Bipolar-Anion-Membranzellenkonfiguration; oder
    (c) einer Kation-Bipolar-Anion-Membranzellkonfiguration.
  12. Verfahren nach einem der vorhergehenden Ansprüche, wobei während der Elektrodialyse ein Anionenaustauschharz in einem Beschickungsraum der Elektrodialysezelle vorliegt.
  13. Verfahren nach Anspruch 11 oder 12, wobei die Elektrodialyse unter Verwendung einer Elektrodialysezelle mit einer von einer Kation-Anion-Membranzellenkonfiguration oder einer Kation-Bipolar-Anion-Membranzellenkonfiguration durchgeführt wird, weiterhin umfassend ein Hinzufügen einer Base zu einem Beschickungsraum in der Elektrodialysezelle.
  14. Verfahren nach einem der vorhergehenden Ansprüche, weiterhin umfassend ein Hinzufügen einer Base zu einer Anionen aufnehmenden Lösung in der Elektrodialysezelle.
  15. Verfahren nach einem der Ansprüche 2 und 4 bis 14, wobei die Säure eine von Schwefelsäure, Salzsäure, Salpetersäure und Phosphorsäure und Gemische davon umfasst.
  16. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung einen Gehalt an suspendierten Feststoffen von mehr als (a) 1.000 mg/l oder (b) 6.000 mg/l aufweist.
EP14884237.0A 2014-02-28 2014-02-28 Reinigungsverfahren für teilweise hydrolysierte cellulose Active EP3110534B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PT148842370T PT3110534T (pt) 2014-02-28 2014-02-28 Processo de purificação para celulose parcialmente hidrolisada

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA2014/050156 WO2015127531A1 (en) 2014-02-28 2014-02-28 Purification process for partly-hydrolyzed cellulose

Publications (3)

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EP3110534A1 EP3110534A1 (de) 2017-01-04
EP3110534A4 EP3110534A4 (de) 2017-10-25
EP3110534B1 true EP3110534B1 (de) 2019-12-25

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US (1) US10016726B2 (de)
EP (1) EP3110534B1 (de)
JP (1) JP6377170B2 (de)
KR (1) KR20160125990A (de)
CN (1) CN106163643B (de)
CA (1) CA2937918C (de)
IL (1) IL247151B (de)
PT (1) PT3110534T (de)
WO (1) WO2015127531A1 (de)

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KR101907868B1 (ko) 2016-12-02 2018-10-15 건국대학교 산학협력단 이온성 액체를 이용한 자기 조립형 균일계 셀룰로오스 나노입자 및 이의 제조 방법
KR102003918B1 (ko) * 2017-11-28 2019-10-17 한국과학기술연구원 에너지 저소비형 당과 산의 분리방법
CN114534500A (zh) * 2022-02-14 2022-05-27 天津大学 一种应用于cnc生产的低浓度废酸分离回收装置及方法
WO2023196233A1 (en) 2022-04-08 2023-10-12 United States Gypsum Company Desalination of high chloride salt absorbed porous beads

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Also Published As

Publication number Publication date
CA2937918A1 (en) 2015-09-03
CN106163643B (zh) 2019-05-07
JP2017508042A (ja) 2017-03-23
EP3110534A4 (de) 2017-10-25
IL247151A0 (en) 2016-09-29
CA2937918C (en) 2021-10-26
JP6377170B2 (ja) 2018-08-22
US10016726B2 (en) 2018-07-10
EP3110534A1 (de) 2017-01-04
US20170014771A1 (en) 2017-01-19
KR20160125990A (ko) 2016-11-01
WO2015127531A1 (en) 2015-09-03
CN106163643A (zh) 2016-11-23
IL247151B (en) 2020-06-30
PT3110534T (pt) 2020-03-05

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